US20180297874A1 - Process for Decontamination of Hazardous Sulfur Compounds in Sour Water Tanks - Google Patents
Process for Decontamination of Hazardous Sulfur Compounds in Sour Water Tanks Download PDFInfo
- Publication number
- US20180297874A1 US20180297874A1 US15/797,492 US201715797492A US2018297874A1 US 20180297874 A1 US20180297874 A1 US 20180297874A1 US 201715797492 A US201715797492 A US 201715797492A US 2018297874 A1 US2018297874 A1 US 2018297874A1
- Authority
- US
- United States
- Prior art keywords
- oxide
- methylmorpholine
- water
- contaminants
- vessel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000005202 decontamination Methods 0.000 title description 5
- 230000003588 decontaminative effect Effects 0.000 title description 5
- 150000003464 sulfur compounds Chemical class 0.000 title description 2
- 231100001261 hazardous Toxicity 0.000 title 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract description 89
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000356 contaminant Substances 0.000 claims abstract description 28
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 58
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 9
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 230000002427 irreversible effect Effects 0.000 claims 3
- 230000007423 decrease Effects 0.000 claims 1
- 239000007787 solid Substances 0.000 description 18
- 238000011282 treatment Methods 0.000 description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- OURXRFYZEOUCRM-UHFFFAOYSA-N 4-hydroxymorpholine Chemical compound ON1CCOCC1 OURXRFYZEOUCRM-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 150000001204 N-oxides Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- 239000012256 powdered iron Substances 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008029 eradication Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 229910052952 pyrrhotite Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- -1 steam Chemical compound 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/04—Metals, or metals deposited on a carrier
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
- C07D265/32—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings with oxygen atoms directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/20—Hydrogen sulfide elimination
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
- C09K8/532—Sulfur
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/80—Additives
- C10G2300/805—Water
- C10G2300/807—Steam
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
- E21B21/06—Arrangements for treating drilling fluids outside the borehole
- E21B21/063—Arrangements for treating drilling fluids outside the borehole by separating components
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/34—Arrangements for separating materials produced by the well
Definitions
- This invention relates to the field of decontamination and more specifically to the field of decontaminating water in vessels using methylmorpholine-N-oxide.
- H 2 S and pyrophoric iron sulfides are commonly contaminated with dangerous and reactive sulfur compounds such as H 2 S and pyrophoric iron sulfides. These compounds are typically mitigated or removed as part of decontamination procedures, for instance, prior to vessel (e.g., large storage tanks) entry by individuals.
- a conventional approach to decontamination is to use hydrogen sulfide scavengers (e.g., liquid scavengers) such as triazine, acrolein, or formaldehyde.
- Such scavengers may rely on non-oxidative complexation and may be an economical approach for H 2 S mitigation.
- Liquid scavengers may tie up H 2 S as water-soluble compounds that may be discharged to wastewater treatment facilities.
- reaction products may not be water-soluble, and some of the treatment chemicals may have associated toxicity or environmental restrictions in certain locations.
- acrolein typically neutralizes pyrophoric iron sulfides.
- Triazine treatments may raise the pH of effluent streams and as a result, may promote the formation of scales on metal surfaces.
- Formaldehyde reactions with H 2 S typically produce water insoluble products.
- Acrolein benefits may be tempered by its toxicity.
- hypochlorite may form dangerous chlorine compounds.
- Ozone and permanganate may require field mixing, and permanganate decontaminations may be further complicated by large amounts of reaction solids that are typically processed at additional cost.
- Sodium nitrite may produce ammonia as a by-product, which may stall the sulfide oxidation before it is complete.
- field mixing or solutions prepared with stabilizing agents are typically used.
- Percarbonates, as with permanganate may also be exothermic in their reaction, which may be particularly dangerous if hydrocarbon vapors are present. It is to be understood that long-chain amine oxides often include large volumes and may produce excessive foam.
- Permanganate produces solid manganese dioxide as a reaction product that is typically processed at added cost.
- Treatments using strong oxidizers are typically accomplished in small sequential batches outside the storage vessel in order to control the associated exotherm. As a result, these treatments may involve considerable time and therefore cost. However, these compounds may also react violently with hydrocarbon components that may be present in sour sludge. Strong oxidizers (i.e., permanganate, percarbonate, persulfate) may be quite non-selective in their reaction and may react with many of the hydrocarbon components that may exist in the sludge that typically is contained in storage vessels. As a result, these type treatments are typically accomplished in small sequential batches outside the vessel in time-consuming fashion.
- Mild oxidizers such as amine oxides and nitrites may also be effective at irreversibly oxidizing hydrogen sulfide to harmless forms of sulfur while having limited or no effect on hydrocarbons, which is unlike the strong oxidizers.
- Such mild oxidizers may normally be added directly to the storage vessel since associated reactions are non-exothermic.
- Such mild oxidizers also have drawbacks. For instance, typical long-chain amine oxides may pose foaming issues due to their surfactancy. These amine oxides may also have limited efficiency for large amounts of H 2 S, since they are typically diluted in water to prevent gel formation.
- Nitrites may also have drawbacks, as their reaction with hydrogen sulfide produces ammonia. As a result, the nitrite oxidation reaction may be accompanied by a rise in pH, which at some point may cease the oxidation before it is complete.
- the method includes introducing a methylmorpholine-N-oxide solution to a vessel.
- the vessel contains the contaminated water and iron oxide.
- the contaminated water comprises contaminants.
- the methylmorpholine-N-oxide solution comprises methylmorpholine-N-oxide and water.
- the method further comprises contacting the methylmorpholine-N-oxide solution with the contaminated water.
- the method comprises treating the contaminated water by allowing the methylmorpholine-N-oxide to react with the contaminants in the presence of the iron oxide.
- FIG. 1 illustrates an embodiment of a methylmorpholine-N-oxide water treatment method
- FIG. 2 illustrates an embodiment of a methylmorpholine-N-oxide water treatment method having a heat exchanger on the recycle
- FIG. 3 illustrates reaction time versus temperature
- FIG. 4 illustrates reaction time versus temperature
- FIG. 1 illustrates an embodiment of methylmorpholine-N-oxide water treatment method 5 .
- methylmorpholine-N-oxide water treatment method 5 treats contaminated water by decontaminating the water by removing a portion or all of the contaminants from the water.
- the contaminated water is disposed in a vessel 10 .
- Vessel 10 may include any type of vessel that may contain water.
- vessel 10 is a tank.
- the water is contaminated with contaminants.
- contaminants include hydrogen sulfide, iron sulfides, or any combinations thereof.
- the contaminant comprises hydrogen sulfide.
- the iron sulfides comprises pyrophoric iron sulfides.
- the pyrophoric iron sulfides may include any pyrophoric iron sulfides.
- the pyrophoric iron sulfides comprise pyrite, troilite, marcasite, pyrrhotite, or any combinations thereof.
- FIG. 1 shows an embodiment of methylmorpholine-N-oxide water treatment method 5 in which methylmorpholine-N-oxide 20 is introduced to vessel 10 .
- Methylmorpholine-N-oxide 20 may be introduced to vessel 10 by any suitable means. Without limitation, examples of such suitable means include a drum pump, tank truck, and the like. Methylmorpholine-N-oxide 20 may be introduced in any suitable form for removing the contaminants from the contaminated water. In embodiments, methylmorpholine-N-oxide 20 is in a methylmorpholine-N-oxide solution comprising methylmorpholine-N-oxide and water.
- the methylmorpholine-N-oxide solutoin may have the methylmorpholine-N-oxide in any desired amount.
- the methylmorpholine-N-oxide may be in a very concentrated form. Without being limited by theory, such very concentrated form may allow the methylmorpholine-N-oxide to be applied in small, efficient amounts.
- the concentrated form may include any desirable concentration.
- the concentration of methylmorpholine-N-oxide in the water is between about 1 weight volume % and about 60 weight volume %, alternatively between about 10 weight volume % and about 20 weight volume %, further alternatively between about 5 weight volume % and about 60 weight volume %, and alternatively between about 50 weight volume % and about 60 weight volume %.
- the concentration of methylmorpholine-N-oxide in the water may be any individual weight volume % in the above ranges or any smaller range of weight volume % that is included in the above ranges. In an embodiment, the concentration of methylmorpholine-N-oxide in the water is between about 50 weight volume % and about 60 weight volume %. In an embodiment, the methylmorpholine-N-oxide is a short-chain amine oxide. In embodiments, the methylmorpholine-N-oxide has the molecular formula C 5 H 11 NO 2 . In vessel 10 , methylmorpholine-N-oxide 20 contacts the contaminated water. In embodimetns, methylmorpholine-N-oxide 20 is not heated before introduction to vessel 10 .
- the amount of methylmorpholine-N-oxide 20 added to vessel 20 provides a mole ratio of methylmorpholine-N-oxide:hydrogen sulfide in vessel 20 from about 1.0 mole methylmorpholine-N-oxide:1.0 mole hydrogen sulfide to about about 3.0 mole methylmorpholine-N-oxide:1.0 mole hydrogen sulfide, or any range or mole ratio therebetween.
- steam 15 is also added to vessel 10 .
- Steam 15 is added to increase the temperature of the contaminated water in vessel 10 .
- steam 15 is added to vessel 10 in amounts to increase the temperature of the contaminated water to a temperature from about 75° F. to about 212° F., alternatively from about 90° F. to about 180° F., and alternatively from about 100° F. to about 140° F.
- the temperature may be any individual temperature in the above ranges or any smaller range of temperatures that is included in the above ranges.
- Any suitable psig steam may be used.
- the steam is 150 psig or less.
- the steam is 50 psig steam or 150 psig steam.
- the methylmorpholine-N-oxide reacts with the contaminants in the presence of iron oxide (i.e., rust).
- iron oxide i.e., rust
- the presence of iron oxide catalyzes the amine oxide (i.e., methylmorpholine-N-oxide) to convert reactive sulfide to elemental sulfur and thiosulfate reaction products irreversibly.
- Any suitable iron oxide may be used.
- the iron oxide includes hydrated iron oxide, anhydrous iron oxide, or any combinations thereof.
- the iron oxide is hydrous iron oxide.
- the iron oxide includes ferrous or ferric oxides that are hydrated.
- the iron oxide is Fe 2 O 3 .7H 2 0, Fe 2 O 3 .10H 2 0, or any combinations thereof.
- the iron oxide may be present in vessel 10 in any amount suitable to catalyze the reaction between the amine oxide and the contaminants.
- vessel 10 has iron oxide in the contaminated water in an amount from about 100 ppm iron oxide to about 1,000 ppm iron oxide.
- the iron oxide may be present in any individual amount in the above range or any smaller range of amounts that is included in the above range.
- no iron oxide is added to vessel 10 as methylmorpholine-N-oxide water treatment method 5 uses the iron oxide already present in vessel 10 . In other embodiments, iron oxide is added to vessel 10 .
- the reaction to remove the contaminants (i.e., reactive sulfide) from the contaminated water comprises methylmorpholine-N-oxide, steam, and iron oxide.
- the reaction is allowed to occur for a sufficient time to allow the contaminants to be removed (i.e., converted) from the water.
- the reaction is allowed to occur from about one hour to about fifty hours, alternatively from about one hour to about twenty-five hours.
- the reaction time may be any individual time in the above times or any smaller time ranges that are included in the above ranges.
- FIG. 3 illustrates examples of reaction time versus temperature. Without being limited by theory, it is to be understood that the higher the temperature, the less reaction time may be used.
- the reaction is allowed to occur for a sufficient time to substantially remove all of the contaminants (i.e., convert substantially all of the reactive sulfide to elemental sulfur). In some embodiments, the reaction produces substantially no foaming. And, in some embodiments, the reaction also does not generate ammonia. In an embodiemnt, the reaction is non-exothermic. In other embodiments, surfactants are not added to the contaminated water or methylmorpholine-N-oxide 20.
- the water 35 (i.e., treated water) may be drawn off from vessel 10 and nonhazardous products 25 may also be removed from vessel 10 .
- Water 35 may be sent to any desired location such as a water treatment plant.
- water 35 has no reactive sulfides.
- Nonhazardous products 25 include nonhazardous sulfur reaction products along with other native solids in vessel 10 (i.e., sludge).
- Nonhazardous products 25 may be removed from vessel 10 by an suitable means.
- the means include a centrifuge.
- the liquid portion of the effluent passing from the centrifuge may then be routed to a treatment facility or any other desirable location.
- steam is not added to vessel 10 .
- methylmorpholine-N-oxide water treatment method 5 may also include re-circulation 30 .
- Re-circulation 30 is re-circulation of contaminated water.
- contaminated water containing introduced methylmorpholine-N-oxide 20 i.e., a mixture of contaminated water and methylmorpholine-N-oxide
- re-circulation 30 facilitates distribution of methylmorpholine-N-oxide 20 in contaminated water.
- re-circulation 30 may include re-circulation of any volume or range of volumes less than two.
- methylmorpholine-N-oxide water treatment method 5 includes heat exchanger 40 , which adds heat to re-circulation 30 . Without limitation, adding the heat increases the reaction.
- Example 1 A purpose of this Example 1 was to determine the extent of reaction of morpholine-N-oxide on H 2 S in sour water at varying mole ratios. The experiments of this Example 1 were conducted at 40° C. and 60° C.
- a morpholine-N-oxide stock solution was prepared by dissolving 5.00 grams in 100.0 mls distilled water (0.397 Ma). To each of several screw-capped sample vials, 2.0 mls of the sour water and a dash of powdered iron rust were added. The vials were then diluted with ⁇ 15 mls of distilled water and the following volumes of morpholine-N-oxide were added.
- each reaction vial was emptied into 20 mls of sulfide anti-oxidant buffer, and each was titrated with 0.100 M/lit Pb ++ , according to ULI Procedure LP1005. The results are shown below.
- Elemental sulfur present as small platelets, had been precipitated during reaction.
- Elemental sulfur present as small platelets, had been precipitated during reaction.
- a purpose of this example was to determine if a lower ratio than 1.0:1.0 of 4-methylmorpholine-N-oxide:sulfide will completely remove sulfide from solution.
- the experiments were conducted at 40° C. and 60° C.
- a pint of archived sour water at pH-8.5 was used and that had an H 2 S content at 8,016 mg/liter (0.250 M/lit).
- a sample of solid 4-methylmorpholine-N-oxide was determined to have a molecular weight of 126.0.
- a 4-methylmorpholine-N-oxide stock solution was prepared by dissolving 5.00 grams in 100.0 mls distilled water (0.397 M/lit). To each of four screw-capped sample vials, 2.0 mls of the sour water and a dash of powdered iron rust were added. The vials were diluted to ⁇ 20 mls with distilled water after adding 0.822 mls of 4-methylmorpholine-N-oxide, which amounted to a reaction ratio of 0.7:1.0.
- the second samples from these reactions were acidified with H 2 SO 4 . This was done in order to determine if there was any odor of residual H 2 S. There was no odor of H 2 S. Instead, there was the unmistakable odor of SO 2 .
- a common reaction product of N-oxides with S ⁇ is thiosulfate. When thiosulfate is acidified, it disproportionates, forming SO 2 .
- Elemental sulfur present as small platelets, had been formed during both reactions.
- a sample of the first tank was taken and found to be black from suspended corrosion solids (Fe 2 O 3 +FeS).
- Various analyses were conducted in order to determine H 2 S content so that a methylmorpholine-N-oxide dose could be calculated.
- Prior readings were 800-900 ppm H 2 S.
- a test using a Chemets sulfide colorimetric test kit estimated 400-500 ppm H 2 S. Iodometric titration gave an H 2 S result of 600-700 ppm on the whole sample, and 400-500 ppm H 2 S on filtered sample.
- the first demonstration was performed under standard conditions where treatments were assisted by heating at 50° C. Two different dosage levels were prepared using newly-made as well as eight month old formulation. One sample was run at ambient conditions. The test make-ups are below in Table 5.
- FIG. 4 illustrates a complete performance summary of methylmorpholine-N-oxide for total H 2 S eradiation under different conditions.
Abstract
Description
- This application is a continuation of U.S. application Ser. No. 14/512,987 filed on Oct. 13, 2014 which is a continuation of U.S. Pat. No. 9,512,019 filed on Oct. 12, 2012 which is a non-provisional that claims the benefit of U.S. Application Ser. No. 61/546,481 filed on Oct. 12, 2011, all of which are incorporated by reference herein in their entirety.
- Not applicable.
- This invention relates to the field of decontamination and more specifically to the field of decontaminating water in vessels using methylmorpholine-N-oxide.
- Refineries and petrochemical plants are commonly contaminated with dangerous and reactive sulfur compounds such as H2S and pyrophoric iron sulfides. These compounds are typically mitigated or removed as part of decontamination procedures, for instance, prior to vessel (e.g., large storage tanks) entry by individuals. A conventional approach to decontamination is to use hydrogen sulfide scavengers (e.g., liquid scavengers) such as triazine, acrolein, or formaldehyde. Such scavengers may rely on non-oxidative complexation and may be an economical approach for H2S mitigation. Liquid scavengers may tie up H2S as water-soluble compounds that may be discharged to wastewater treatment facilities. However, such scavengers have drawbacks. For instance, some of the reaction products may not be water-soluble, and some of the treatment chemicals may have associated toxicity or environmental restrictions in certain locations. In addition, only acrolein typically neutralizes pyrophoric iron sulfides. Triazine treatments may raise the pH of effluent streams and as a result, may promote the formation of scales on metal surfaces. Formaldehyde reactions with H2S typically produce water insoluble products. Acrolein benefits may be tempered by its toxicity.
- Other methods have been developed and demonstrated to be effective at oxidizing and eliminating H2S and pyrophoric iron sulfide. Such methods include using permanganate (e.g., potassium permanganate), persulfate, sodium nitrite, ozone, hypochlorite, adducts of peroxide such as perborates and percarbonates, and long-chain amine oxides. The oxidizing chemicals may irreversibly convert H2S to harmless water soluble forms of sulfur, which may be compatible with effluent discharge. Each of these scavengers and oxidizing compounds (i.e., oxidizing chemicals) have certain drawbacks. For instance, considering the strong oxidizers, persulfates may be corrosive. Hypochlorite may form dangerous chlorine compounds. Ozone and permanganate may require field mixing, and permanganate decontaminations may be further complicated by large amounts of reaction solids that are typically processed at additional cost. Sodium nitrite may produce ammonia as a by-product, which may stall the sulfide oxidation before it is complete. For perborates and percarbonates, field mixing or solutions prepared with stabilizing agents are typically used. Percarbonates, as with permanganate, may also be exothermic in their reaction, which may be particularly dangerous if hydrocarbon vapors are present. It is to be understood that long-chain amine oxides often include large volumes and may produce excessive foam. Permanganate produces solid manganese dioxide as a reaction product that is typically processed at added cost. Treatments using strong oxidizers are typically accomplished in small sequential batches outside the storage vessel in order to control the associated exotherm. As a result, these treatments may involve considerable time and therefore cost. However, these compounds may also react violently with hydrocarbon components that may be present in sour sludge. Strong oxidizers (i.e., permanganate, percarbonate, persulfate) may be quite non-selective in their reaction and may react with many of the hydrocarbon components that may exist in the sludge that typically is contained in storage vessels. As a result, these type treatments are typically accomplished in small sequential batches outside the vessel in time-consuming fashion.
- Mild oxidizers such as amine oxides and nitrites may also be effective at irreversibly oxidizing hydrogen sulfide to harmless forms of sulfur while having limited or no effect on hydrocarbons, which is unlike the strong oxidizers. Such mild oxidizers may normally be added directly to the storage vessel since associated reactions are non-exothermic. Such mild oxidizers also have drawbacks. For instance, typical long-chain amine oxides may pose foaming issues due to their surfactancy. These amine oxides may also have limited efficiency for large amounts of H2S, since they are typically diluted in water to prevent gel formation. Nitrites may also have drawbacks, as their reaction with hydrogen sulfide produces ammonia. As a result, the nitrite oxidation reaction may be accompanied by a rise in pH, which at some point may cease the oxidation before it is complete.
- Consequently, there is a need for improved methods and products for decontaminating vessels such as sour water tanks.
- These and other needs in the art are addressed in one embodiment by a method for treating contaminated water. The method includes introducing a methylmorpholine-N-oxide solution to a vessel. The vessel contains the contaminated water and iron oxide. The contaminated water comprises contaminants. The methylmorpholine-N-oxide solution comprises methylmorpholine-N-oxide and water. The method further comprises contacting the methylmorpholine-N-oxide solution with the contaminated water. In addition, the method comprises treating the contaminated water by allowing the methylmorpholine-N-oxide to react with the contaminants in the presence of the iron oxide.
- The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter that form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and the specific embodiments disclosed may be readily utilized as a basis for modifying or designing other embodiments for carrying out the same purposes of the present invention. It should also be realized by those skilled in the art that such equivalent embodiments do not depart from the spirit and scope of the invention as set forth in the appended claims.
- For a detailed description of the preferred embodiments of the invention, reference will now be made to the accompanying drawings in which:
-
FIG. 1 illustrates an embodiment of a methylmorpholine-N-oxide water treatment method; -
FIG. 2 illustrates an embodiment of a methylmorpholine-N-oxide water treatment method having a heat exchanger on the recycle; -
FIG. 3 illustrates reaction time versus temperature; and -
FIG. 4 illustrates reaction time versus temperature. -
FIG. 1 illustrates an embodiment of methylmorpholine-N-oxidewater treatment method 5. In an embodiment, methylmorpholine-N-oxidewater treatment method 5 treats contaminated water by decontaminating the water by removing a portion or all of the contaminants from the water. - In embodiments as shown in
FIG. 1 , the contaminated water is disposed in avessel 10.Vessel 10 may include any type of vessel that may contain water. In an embodiment,vessel 10 is a tank. In embodiments, the water is contaminated with contaminants. Without limitation, examples of contaminants include hydrogen sulfide, iron sulfides, or any combinations thereof. In an embodiment, the contaminant comprises hydrogen sulfide. In some embodiments, the iron sulfides comprises pyrophoric iron sulfides. The pyrophoric iron sulfides may include any pyrophoric iron sulfides. In embodiments, the pyrophoric iron sulfides comprise pyrite, troilite, marcasite, pyrrhotite, or any combinations thereof. -
FIG. 1 shows an embodiment of methylmorpholine-N-oxidewater treatment method 5 in which methylmorpholine-N-oxide 20 is introduced tovessel 10. Methylmorpholine-N-oxide 20 may be introduced tovessel 10 by any suitable means. Without limitation, examples of such suitable means include a drum pump, tank truck, and the like. Methylmorpholine-N-oxide 20 may be introduced in any suitable form for removing the contaminants from the contaminated water. In embodiments, methylmorpholine-N-oxide 20 is in a methylmorpholine-N-oxide solution comprising methylmorpholine-N-oxide and water. The methylmorpholine-N-oxide solutoin may have the methylmorpholine-N-oxide in any desired amount. In some embodiments, the methylmorpholine-N-oxide may be in a very concentrated form. Without being limited by theory, such very concentrated form may allow the methylmorpholine-N-oxide to be applied in small, efficient amounts. The concentrated form may include any desirable concentration. In an embodiment, the concentration of methylmorpholine-N-oxide in the water is between about 1 weight volume % and about 60 weight volume %, alternatively between about 10 weight volume % and about 20 weight volume %, further alternatively between about 5 weight volume % and about 60 weight volume %, and alternatively between about 50 weight volume % and about 60 weight volume %. In embodiments, the concentration of methylmorpholine-N-oxide in the water may be any individual weight volume % in the above ranges or any smaller range of weight volume % that is included in the above ranges. In an embodiment, the concentration of methylmorpholine-N-oxide in the water is between about 50 weight volume % and about 60 weight volume %. In an embodiment, the methylmorpholine-N-oxide is a short-chain amine oxide. In embodiments, the methylmorpholine-N-oxide has the molecular formula C5H11NO2. Invessel 10, methylmorpholine-N-oxide 20 contacts the contaminated water. In embodimetns, methylmorpholine-N-oxide 20 is not heated before introduction tovessel 10. In embodiments, the amount of methylmorpholine-N-oxide 20 added tovessel 20 provides a mole ratio of methylmorpholine-N-oxide:hydrogen sulfide invessel 20 from about 1.0 mole methylmorpholine-N-oxide:1.0 mole hydrogen sulfide to about about 3.0 mole methylmorpholine-N-oxide:1.0 mole hydrogen sulfide, or any range or mole ratio therebetween. - In further embodiments as shown in
FIG. 1 ,steam 15 is also added tovessel 10.Steam 15 is added to increase the temperature of the contaminated water invessel 10. In embodiments,steam 15 is added tovessel 10 in amounts to increase the temperature of the contaminated water to a temperature from about 75° F. to about 212° F., alternatively from about 90° F. to about 180° F., and alternatively from about 100° F. to about 140° F. In embodiments, the temperature may be any individual temperature in the above ranges or any smaller range of temperatures that is included in the above ranges. Any suitable psig steam may be used. In embodiments, the steam is 150 psig or less. In an embodiment, the steam is 50 psig steam or 150 psig steam. - In embodiments, the methylmorpholine-N-oxide reacts with the contaminants in the presence of iron oxide (i.e., rust). Without being limited by theory, the presence of iron oxide catalyzes the amine oxide (i.e., methylmorpholine-N-oxide) to convert reactive sulfide to elemental sulfur and thiosulfate reaction products irreversibly. Any suitable iron oxide may be used. In embodiments, the iron oxide includes hydrated iron oxide, anhydrous iron oxide, or any combinations thereof. In an embodiment, the iron oxide is hydrous iron oxide. In embodiments, the iron oxide includes ferrous or ferric oxides that are hydrated. In an embodiment, the iron oxide is Fe2O3.7H20, Fe2O3.10H20, or any combinations thereof. The iron oxide may be present in
vessel 10 in any amount suitable to catalyze the reaction between the amine oxide and the contaminants. In an embodiment,vessel 10 has iron oxide in the contaminated water in an amount from about 100 ppm iron oxide to about 1,000 ppm iron oxide. In embodiments, the iron oxide may be present in any individual amount in the above range or any smaller range of amounts that is included in the above range. In embodiments, no iron oxide is added tovessel 10 as methylmorpholine-N-oxidewater treatment method 5 uses the iron oxide already present invessel 10. In other embodiments, iron oxide is added tovessel 10. Without being limted by theory, the reaction to remove the contaminants (i.e., reactive sulfide) from the contaminated water comprises methylmorpholine-N-oxide, steam, and iron oxide. The reaction is allowed to occur for a sufficient time to allow the contaminants to be removed (i.e., converted) from the water. In embodiments, the reaction is allowed to occur from about one hour to about fifty hours, alternatively from about one hour to about twenty-five hours. In embodiments, the reaction time may be any individual time in the above times or any smaller time ranges that are included in the above ranges.FIG. 3 illustrates examples of reaction time versus temperature. Without being limited by theory, it is to be understood that the higher the temperature, the less reaction time may be used. In embodiments, the reaction is allowed to occur for a sufficient time to substantially remove all of the contaminants (i.e., convert substantially all of the reactive sulfide to elemental sulfur). In some embodiments, the reaction produces substantially no foaming. And, in some embodiments, the reaction also does not generate ammonia. In an embodiemnt, the reaction is non-exothermic. In other embodiments, surfactants are not added to the contaminated water or methylmorpholine-N-oxide 20. - After the desired reaction time occurs (i.e., sulfide conversion is about complete), the water 35 (i.e., treated water) may be drawn off from
vessel 10 andnonhazardous products 25 may also be removed fromvessel 10.Water 35 may be sent to any desired location such as a water treatment plant. In embodiments,water 35 has no reactive sulfides.Nonhazardous products 25 include nonhazardous sulfur reaction products along with other native solids in vessel 10 (i.e., sludge).Nonhazardous products 25 may be removed fromvessel 10 by an suitable means. In an embodiment, the means include a centrifuge. In embodiments, the liquid portion of the effluent passing from the centrifuge may then be routed to a treatment facility or any other desirable location. - In some embodiments (not illustrated), steam is not added to
vessel 10. - In an embodiment as shown in
FIG. 1 , methylmorpholine-N-oxidewater treatment method 5 may also includere-circulation 30.Re-circulation 30 is re-circulation of contaminated water. In some embodiments, contaminated water containing introduced methylmorpholine-N-oxide 20 (i.e., a mixture of contaminated water and methylmorpholine-N-oxide) is re-circulated. Without limitation, re-circulation 30 facilitates distribution of methylmorpholine-N-oxide 20 in contaminated water. In an embodiment, from about one volume of the toal amount of contaminated water and methylmorpholine-N-oxide solution invessel 10 to about twovessel 10 volumes of the total amount of contaminated water and methylmorpholine-N-oxide solution invessel 10 are re-circulated. In embodiments, re-circulation 30 may include re-circulation of any volume or range of volumes less than two. - In embodiments as shown in
FIG. 2 , methylmorpholine-N-oxidewater treatment method 5 includesheat exchanger 40, which adds heat tore-circulation 30. Without limitation, adding the heat increases the reaction. - To further illustrate various illustrative embodiments of the present invention, the following examples are provided.
- A purpose of this Example 1 was to determine the extent of reaction of morpholine-N-oxide on H2S in sour water at varying mole ratios. The experiments of this Example 1 were conducted at 40° C. and 60° C.
- At all mole ratios (morpholine-N-oxide:H2S) down to and including 1.0:1.0, the destruction of H2S was complete at 60° C. after 24 hours. Elemental sulfur was a visible product. This S° was present as platelets (“flakes”).
- After 24 hours at 40° C., the reaction was complete only at a mole ratio of 3.0:1.0, although nearly complete reactions were recorded at ratios of 2.0:1.0 and 1.8:1.0. Reactions at lower mole ratios were variously incomplete and consistent with the lower loadings.
- After 48 hours at 40° C., the reaction was complete at all mole ratios except for the lowest loading (1.0:1.0). The product S° was variously present as a milky suspension and flaked solids.
- For the experiment, a pint of archived sour water at pH˜8.5 was used with an H2S content at 9,985 mg/liter (0.293 M/lit). The molecular weight of the solid morpholine-N-oxide was 126.0.
- A morpholine-N-oxide stock solution was prepared by dissolving 5.00 grams in 100.0 mls distilled water (0.397 Ma). To each of several screw-capped sample vials, 2.0 mls of the sour water and a dash of powdered iron rust were added. The vials were then diluted with ˜15 mls of distilled water and the following volumes of morpholine-N-oxide were added.
-
TABLE 1 Sample Makeup [Morpholine-N-oxide] = 0.397 M/lit [H2S] = 0.293 M/lit (@ pH~8.5) ~0.5 gm Fe2O3•xH2O Volume morpholine- Mole ratio N-oxide stock (N-oxide:H2S) 1.477 mls 1.0:1 1.772 mls 1.2:1 2.067 mls 1.4:1 2.363 mls 1.6:1 2.658 mls 1.8:1 2.953 mls 2.0:1 4.430 mls 3.0:1 - Three such series were prepared. Each series was treated as follows: series 1: heated at 40° C. for 24 hours (static), series 2: heated at 40° C. for 48 hours (static), series 3: heated at 60° C. for 24 hours (static).
- At termination of the reaction periods, the entire contents of each reaction vial were emptied into 20 mls of sulfide anti-oxidant buffer, and each was titrated with 0.100 M/lit Pb++, according to ULI Procedure LP1005. The results are shown below.
-
TABLE 2 Reaction of Morpholine-N-oxide on H2S for 24 Hours @ 40° C. Sample mls Pb++ Gms H2S Titrated Gms H2S Added % Reacted 1.0:1 1.9 0.00019 0.000585 68% 1.2:1 1.8 0.00018 0.000585 69% 1.4:1 1.7 0.00017 0.000585 71% 1.6:1 0.7 0.00007 0.000585 88% 1.8:1 0.4 0.00004 0.000585 93% 2.0:1 0.3 0.00003 0.000585 95% 3.0:1 0.0 0.00000 0.000585 100% -
TABLE 3 Reaction of Morpholine-N-oxide on H2S for 48 Hours @ 40° C. Sample mls Pb++ Gms H2S Titrated Gms H2S Added % Reacted 1.0:1 0.4 0.00004 0.000585 93% 1.2:1 0.0 0.00000 0.000585 100% 1.4:1 0.0 0.00000 0.000585 100% 1.6:1 0.0 0.00000 0.000585 100% 1.8:1 0.0 0.00000 0.000585 100% 2.0:1 0.0 0.00000 0.000585 100% 3.0:1 0.0 0.00000 0.000585 100% - Elemental sulfur, present as small platelets, had been precipitated during reaction.
-
TABLE 4 Reaction of Morpholine-N-oxide on H2S for 24 Hours @ 60° C. Sample mls Pb++ Gms H2S Titrated Gms H2S Added % Reacted 1.0:1 0.0 0.00000 0.000585 100% 1.2:1 0.0 0.00000 0.000585 100% 1.4:1 0.0 0.00000 0.000585 100% 1.6:1 0.0 0.00000 0.000585 100% 1.8:1 0.0 0.00000 0.000585 100% 2.0:1 0.0 0.00000 0.000585 100% 3.0:1 0.0 0.00000 0.000585 100% - Elemental sulfur, present as small platelets, had been precipitated during reaction.
- A purpose of this example was to determine if a lower ratio than 1.0:1.0 of 4-methylmorpholine-N-oxide:sulfide will completely remove sulfide from solution. The experiments were conducted at 40° C. and 60° C.
- At a mole ratio of 0.7:1.0 (N-oxide:sulfide), the oxidation and removal of sulfide appeared to be 98%-99% complete.
- A pint of archived sour water at pH-8.5 was used and that had an H2S content at 8,016 mg/liter (0.250 M/lit). A sample of solid 4-methylmorpholine-N-oxide was determined to have a molecular weight of 126.0.
- A 4-methylmorpholine-N-oxide stock solution was prepared by dissolving 5.00 grams in 100.0 mls distilled water (0.397 M/lit). To each of four screw-capped sample vials, 2.0 mls of the sour water and a dash of powdered iron rust were added. The vials were diluted to ˜20 mls with distilled water after adding 0.822 mls of 4-methylmorpholine-N-oxide, which amounted to a reaction ratio of 0.7:1.0.
- Two of the samples were placed in a 40° C. bath for a reaction time of 48 hours. The other two were placed in a 60° C. bath for 24 hours. At termination of the reaction periods, the entire contents of a reaction vial from each bath were emptied into 20 mls of sulfide anti-oxidant buffer and each was titrated with 0.100 M/lit Pb++, according to ULI Procedure LP1005.
- The sample reacted at 40° C. required 0.10 mls of the Pb titrant, and the sample reacted at 60° C. required 0.05 mls. These analysis results calculated to 99% and 98% destruction of sulfide in the tests.
- The second samples from these reactions were acidified with H2SO4. This was done in order to determine if there was any odor of residual H2S. There was no odor of H2S. Instead, there was the unmistakable odor of SO2. A common reaction product of N-oxides with S═ is thiosulfate. When thiosulfate is acidified, it disproportionates, forming SO2.
- Elemental sulfur, present as small platelets, had been formed during both reactions.
- Two large sour water tanks (about 20,000 m3) were respectively 80% and 75% filled. Methylmorpholine-N-oxide with added temperature of 50° C. was found to reduce hydrogen sulfide to 0 ppm in 19 hours or less.
- During the course of testing, discoveries were made about the catalytic effect of the voluminous corrosion solids in the tank. When such solids were present, methylmorpholine-N-oxide trials at ambient temperatures were found to be complete with hydrogen sulfide at 0 ppm after 24 hours treatment time. Other trials where the solids were removed prior to methylmorpholine-N-oxide treatment demonstrated that methylmorpholine-N-oxide reduced hydrogen sulfide to 0 ppm in six days at ambient conditions.
- A sample of the first tank was taken and found to be black from suspended corrosion solids (Fe2O3+FeS). Various analyses were conducted in order to determine H2S content so that a methylmorpholine-N-oxide dose could be calculated. Prior readings were 800-900 ppm H2S. A test using a Chemets sulfide colorimetric test kit estimated 400-500 ppm H2S. Iodometric titration gave an H2S result of 600-700 ppm on the whole sample, and 400-500 ppm H2S on filtered sample.
- The first demonstration was performed under standard conditions where treatments were assisted by heating at 50° C. Two different dosage levels were prepared using newly-made as well as eight month old formulation. One sample was run at ambient conditions. The test make-ups are below in Table 5.
-
TABLE 5 First methylmorpholine-N- Temp Tank oxide: H2S mole ratio (° C.) Start 15 1.5:1 50 14:30 15 3:1 50 14:30 15 3:1 50 14:30 15 3:1 50 14:30 - After 19 hours under the test conditions described above, the heated samples were observed to be completely reacted (H2S=0 ppm). Also, the ambient sample was mostly reacted as evidenced by a cloudy yellow solution, which is typical for that course of the reaction.
- Verification of the completion of H2S oxidation was seen in the lead acetate test strips. A dark strip was untreated, the clear strip included the three heated samples with H2S=0 ppm, and another strip was the ambient sample that was seen to be much lighter. A subsequent test with Chemets colorimetric sulfide kit indicated the H2S levels in the ambient sample to be well below 100 ppm H2S.
- The ambient tests were surprising. This test suggested that the presence of significant amounts of corrosion material were such a sufficient catalyst for timely methylmorpholine-N-oxide reaction that heat was not necessary.
- Lab trials were initiated to study the effectiveness of methylmorpholine-N-oxide at low dose rates and under ambient conditions. The sample array was intended to study the reaction rate of methylmorpholine-N-oxide with and without the catalytic solids and also varying dose rates. One sample represented the most extreme test of methylmorpholine-N-oxide—ambient conditions with no solids present and a methylmorpholine-N-oxide: H2S ratio of 1:1 (i.e., the lowest theoretical dose rate possible). Test parameters were summarized in Table 6.
-
TABLE 6 Mole ratio methylmorpholine-N- oxide:H2S Solids Level Temperature Start 1:1 Minimal Ambient 10:00 1.5:1 Minimal Ambient 10:00 1.5:1 Abundant-Sx Shaken Ambient 10:00 - After 24 hours of exposure, methylmorpholine-N-oxide was found to produce complete eradication of H2S in the sample with solids as evidenced. This was consistent with the ambient test with solids above. Also, the higher dose sample with no solids looked to be turning a darker shade of yellow, which indicated some initial progress in reaction.
- Both of the samples with no solids present were also seen to progressively react with all the H2S as well, at much longer reaction times. A summary of the results is included in Table 7.
-
TABLE 7 Solids Present Mole Ratio Time to H2S = 0 ppm Yes 1.5:1 24 hours No 1.5:1 6 days No 1:1 (theoretical minimum) 12 days -
FIG. 4 illustrates a complete performance summary of methylmorpholine-N-oxide for total H2S eradiation under different conditions. - Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations may be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (20)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/797,492 US10745303B2 (en) | 2011-10-12 | 2017-10-30 | Process for decontamination of hazardous sulfur compounds in sour water tanks |
US16/996,800 US11753320B2 (en) | 2011-10-12 | 2020-08-18 | Process for decontamination of hazardous sulfur compounds in sour water tanks |
US18/367,348 US20240067543A1 (en) | 2011-10-12 | 2023-09-12 | Process for Decontamination of Hazardous Sulfur Compounds in Sour Water Tanks |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161546481P | 2011-10-12 | 2011-10-12 | |
US13/650,561 US9512019B2 (en) | 2011-10-12 | 2012-10-12 | Process for decontamination of hazardous sulfur compounds in sour water tanks |
US14/512,987 US9815720B2 (en) | 2011-10-12 | 2014-10-13 | Process for decontamination of hazardous sulfur compounds in sour water tanks |
US15/797,492 US10745303B2 (en) | 2011-10-12 | 2017-10-30 | Process for decontamination of hazardous sulfur compounds in sour water tanks |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/512,987 Continuation US9815720B2 (en) | 2011-10-12 | 2014-10-13 | Process for decontamination of hazardous sulfur compounds in sour water tanks |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/996,800 Continuation US11753320B2 (en) | 2011-10-12 | 2020-08-18 | Process for decontamination of hazardous sulfur compounds in sour water tanks |
Publications (2)
Publication Number | Publication Date |
---|---|
US20180297874A1 true US20180297874A1 (en) | 2018-10-18 |
US10745303B2 US10745303B2 (en) | 2020-08-18 |
Family
ID=48082486
Family Applications (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/650,561 Active US9512019B2 (en) | 2011-10-12 | 2012-10-12 | Process for decontamination of hazardous sulfur compounds in sour water tanks |
US14/512,987 Active 2033-08-01 US9815720B2 (en) | 2011-10-12 | 2014-10-13 | Process for decontamination of hazardous sulfur compounds in sour water tanks |
US15/797,492 Active 2033-02-21 US10745303B2 (en) | 2011-10-12 | 2017-10-30 | Process for decontamination of hazardous sulfur compounds in sour water tanks |
US16/996,800 Active US11753320B2 (en) | 2011-10-12 | 2020-08-18 | Process for decontamination of hazardous sulfur compounds in sour water tanks |
US18/367,348 Pending US20240067543A1 (en) | 2011-10-12 | 2023-09-12 | Process for Decontamination of Hazardous Sulfur Compounds in Sour Water Tanks |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/650,561 Active US9512019B2 (en) | 2011-10-12 | 2012-10-12 | Process for decontamination of hazardous sulfur compounds in sour water tanks |
US14/512,987 Active 2033-08-01 US9815720B2 (en) | 2011-10-12 | 2014-10-13 | Process for decontamination of hazardous sulfur compounds in sour water tanks |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/996,800 Active US11753320B2 (en) | 2011-10-12 | 2020-08-18 | Process for decontamination of hazardous sulfur compounds in sour water tanks |
US18/367,348 Pending US20240067543A1 (en) | 2011-10-12 | 2023-09-12 | Process for Decontamination of Hazardous Sulfur Compounds in Sour Water Tanks |
Country Status (5)
Country | Link |
---|---|
US (5) | US9512019B2 (en) |
EP (1) | EP2766312A4 (en) |
AU (2) | AU2012322060C1 (en) |
CA (1) | CA2855945C (en) |
WO (1) | WO2013056035A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8993488B2 (en) | 2011-02-24 | 2015-03-31 | United Laboratories International, Llc | Process for removal of hydrogen sulfide in downhole oilfield applications |
AU2012322060C1 (en) * | 2011-10-12 | 2017-11-16 | United Laboratories International, Llc | Process for decontamination of hazardous sulfur compounds in sour water tanks |
US10093869B2 (en) * | 2015-09-21 | 2018-10-09 | United Laboratories International, Llc | Decontamination of sulfur contaminants from hydrocarbons |
US10052583B2 (en) | 2015-09-21 | 2018-08-21 | United Laboratories International, Llc | Decontamination of sulfur contaminants from a vessel |
RU2641910C1 (en) * | 2017-01-27 | 2018-01-23 | Игорь Валентинович Исиченко | Process of cleaning hydrocarbon media from h2s and/or mercaptanes |
CN113019078B (en) * | 2021-03-17 | 2023-01-10 | 青岛科技大学 | Morpholine iron-based ionic liquid and application thereof in removing hydrogen sulfide in gas |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5820766A (en) * | 1997-04-23 | 1998-10-13 | Phillips Petroleum Company | Reduction of sulfide in fluids |
US5980733A (en) * | 1994-04-15 | 1999-11-09 | United Laboratories International | Method of removing sulfur compounds from hydrocarbon streams |
US20080053920A1 (en) * | 2004-04-21 | 2008-03-06 | Bj Services Company | Scavenging hydrogen sulfide and/or mercaptans from fluid and gas streams |
US20110272365A1 (en) * | 2010-05-07 | 2011-11-10 | Encana Corporation | Removal of hydrogen sulfide from water |
US20130140243A1 (en) * | 2010-05-06 | 2013-06-06 | Bert Gustafsson | Method and Plant for Purifying Raw Water |
US8993488B2 (en) * | 2011-02-24 | 2015-03-31 | United Laboratories International, Llc | Process for removal of hydrogen sulfide in downhole oilfield applications |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT392776B (en) * | 1989-10-16 | 1991-06-10 | Chemiefaser Lenzing Ag | METHOD FOR PURIFYING AQUEOUS SOLUTIONS OF N-METHYLMORPHOLIN-N-OXIDE |
KR0125960B1 (en) | 1994-04-27 | 1997-12-24 | 김은영 | Method for the purification of reclaimed aqueous n-methyl morpholine n-oxide solution |
US6221277B1 (en) * | 1997-02-18 | 2001-04-24 | The Sulfatreat Company | Composition for removing sulfur compounds from fluids |
US5967230A (en) * | 1997-11-14 | 1999-10-19 | Cooper; Kent | In situ water and soil remediation method and system |
KR100921261B1 (en) * | 2001-12-04 | 2009-10-09 | 토다 고교 가부시끼가이샤 | Iron Particles for Purifying Contaminated Soil or Ground Water, Process for Producing the Iron Particles, Purifying Agent Comprising the Iron Particles, Process for Producing the Purifying Agent and Method of Purifying Contaminated Soil or Ground Water |
US7204967B2 (en) * | 2005-08-26 | 2007-04-17 | Bierle Scott A | Waste water process with scrubber |
AU2012322060C1 (en) | 2011-10-12 | 2017-11-16 | United Laboratories International, Llc | Process for decontamination of hazardous sulfur compounds in sour water tanks |
-
2012
- 2012-10-12 AU AU2012322060A patent/AU2012322060C1/en active Active
- 2012-10-12 WO PCT/US2012/059934 patent/WO2013056035A1/en active Application Filing
- 2012-10-12 EP EP12839497.0A patent/EP2766312A4/en not_active Withdrawn
- 2012-10-12 US US13/650,561 patent/US9512019B2/en active Active
- 2012-10-12 CA CA2855945A patent/CA2855945C/en active Active
-
2014
- 2014-10-13 US US14/512,987 patent/US9815720B2/en active Active
-
2017
- 2017-07-20 AU AU2017206259A patent/AU2017206259B2/en active Active
- 2017-10-30 US US15/797,492 patent/US10745303B2/en active Active
-
2020
- 2020-08-18 US US16/996,800 patent/US11753320B2/en active Active
-
2023
- 2023-09-12 US US18/367,348 patent/US20240067543A1/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5980733A (en) * | 1994-04-15 | 1999-11-09 | United Laboratories International | Method of removing sulfur compounds from hydrocarbon streams |
US5820766A (en) * | 1997-04-23 | 1998-10-13 | Phillips Petroleum Company | Reduction of sulfide in fluids |
US20080053920A1 (en) * | 2004-04-21 | 2008-03-06 | Bj Services Company | Scavenging hydrogen sulfide and/or mercaptans from fluid and gas streams |
US20130140243A1 (en) * | 2010-05-06 | 2013-06-06 | Bert Gustafsson | Method and Plant for Purifying Raw Water |
US20110272365A1 (en) * | 2010-05-07 | 2011-11-10 | Encana Corporation | Removal of hydrogen sulfide from water |
US8993488B2 (en) * | 2011-02-24 | 2015-03-31 | United Laboratories International, Llc | Process for removal of hydrogen sulfide in downhole oilfield applications |
Also Published As
Publication number | Publication date |
---|---|
AU2017206259A1 (en) | 2017-08-10 |
US20240067543A1 (en) | 2024-02-29 |
EP2766312A1 (en) | 2014-08-20 |
AU2012322060A1 (en) | 2014-05-29 |
EP2766312A4 (en) | 2015-09-09 |
US9815720B2 (en) | 2017-11-14 |
US20200377394A1 (en) | 2020-12-03 |
US20150027961A1 (en) | 2015-01-29 |
US20130126444A1 (en) | 2013-05-23 |
US11753320B2 (en) | 2023-09-12 |
AU2012322060C1 (en) | 2017-11-16 |
US10745303B2 (en) | 2020-08-18 |
CA2855945A1 (en) | 2013-04-18 |
CA2855945C (en) | 2018-02-27 |
US9512019B2 (en) | 2016-12-06 |
WO2013056035A1 (en) | 2013-04-18 |
AU2017206259B2 (en) | 2019-11-14 |
AU2012322060B2 (en) | 2017-08-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11753320B2 (en) | Process for decontamination of hazardous sulfur compounds in sour water tanks | |
US11850551B2 (en) | Decontamination of sulfur contaminants from a vessel | |
US11236262B2 (en) | Process for removal of hydrogen sulfide in downhole oilfield application | |
US11427769B2 (en) | Decontamination of sulfur contaminants from hydrocarbons | |
US10723641B2 (en) | Sodium nitrite oxidation of hydrogen sulfide | |
Mamat et al. | Oxidation of sulfide removal from petroleum refinery wastewater by using hydrogen peroxide | |
BACHELOR | Advanced Oxidation Process of Methyldiethanolamine in wastewater |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FEPP | Fee payment procedure |
Free format text: ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: BIG.); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY |
|
FEPP | Fee payment procedure |
Free format text: ENTITY STATUS SET TO SMALL (ORIGINAL EVENT CODE: SMAL); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY |
|
AS | Assignment |
Owner name: UNITED LABORATORIES INTERNATIONAL, LLC, TEXAS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MATZA, STEPHEN D;FROST, JACK G;SIGNING DATES FROM 20131121 TO 20131123;REEL/FRAME:045187/0148 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FEPP | Fee payment procedure |
Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY |